Amines sulfides

Sulfonyloxazindines as aprollc neutral oxidizing reagents oxidainn of amines, sulfides, selenides and asymmetric oxidation. 

Generally, isolated olefinic bonds will not escape attack by these reagents. However, in certain cases where the rate of hydroxyl oxidation is relatively fast, as with allylic alcohols, an isolated double bond will survive. Thepresence of other nucleophilic centers in the molecule, such as primary and secondary amines, sulfides, enol ethers and activated aromatic systems, will generate undesirable side reactions, but aldehydes, esters, ethers, ketals and acetals are generally stable under neutral or basic conditions. Halogenation of the product ketone can become but is not always a problem when base is not included in the reaction mixture. The generated acid can promote formation of an enol which in turn may compete favorably with the alcohol for the oxidant. 

The reactions with nucleophiles include a wide variety such as amines, sulfides (133,135), diazomethane (111), and others. Of particular interest were the reactions of such intermediate iminium salts with 2,3-dimethyl-butadiene to give cyclic products as shown in the reaction of N-bromo-methylpiperidine and N-bromo- and N-chloromethyldiethylamine (134). 

Gold nanoparticles stabilized by primary amine, tertiary amine, sulfide, and thiols... 

Scheme 2. Production of size-regulated gold nanoparticles stabilized by primary amines, tertiary amines, sulfides, and thiols formed by the controlled thermolysis of gold(I) thiolate complex in the presence of amine (reprinted from Ref. [11], 2005, with permission from Elsevier).

Complexes of tetravalent zirconium with organic acids, such as citric, tartaric, malic, and lactic acids, and a complex of aluminum and citric acid have been claimed to be active as dispersants. The dispersant is especially useful in dispersing bentonite suspensions [288]. Polymers with amine sulfide terminal moieties are synthesized by using aminethiols as chain transfer agents in aqueous addition polymerizations. The polymers are useful as mineral dispersants [1182]. 

Polymers with Amine Sulfide Terminal Moieties... 

Several nitro compounds are soluble in chlorine trifluoride, but the solutions are extremely shock-sensitive. These include trinitrotoluene, hexanitrobiphenyl, hexanitrodiphenyl-amine, -sulfide or -ether. Highly chlorinated compounds behave similarly. 

Heterolytic catalysis is promoted by W6+, Ti4+, Cr3+, V5+, and many Mo6+ complexes. These complexes do not normally react with peroxides. However, in the presence of electron-rich molecules, such as alkenes, amines, sulfides, etc., oxygen insertion in the reactant occurs. For example,... 

A wide variety of cyclic monomers have been successfully polymerized by the ring-opening process [Frisch and Reegan, 1969 Ivin and Saegusa, 1984 Saegusa and Goethals, 1977]. This includes cyclic amines, sulfides, olefins, cyclotriphosphazenes, and IV-carboxy-oc-amino acid anhydrides, in addition to those classes of monomers mentioned above. The ease of polymerization of a cyclic monomer depends on both thermodynamic and kinetic factors as previously discussed in Sec. 2-5. 

While it is well established that HO—ONO can be involved in such two-electron processes as alkene epoxidation and the oxidation of amines, sulfides and phosphines, the controversy remains concerning the mechanism of HO-ONO oxidation of saturated hydrocarbons. Rank and coworkers advanced the hypothesis that the reactive species in hydrocarbon oxidations by peroxynitrous acid, and in lipid peroxidation in the presence of air, is the discrete hydroxyl radical formed in the homolysis of HO—ONO. The HO—ONO oxidation of methane (equation 7) on the restricted surface with the B3LYP and QCISD methods gave about the same activation energy (31 3 kcalmol" ) irrespective of basis set size . ... 

The oxidation of a heteroatom bearing a lone pair of electrons (e.g. amine, sulfide or phosphine) with increased nucleophilicity of the heteroatom typically results in an early TS, especially with phosphines. Since the N—O bond in an N-oxide is particularly weak, this can sometimes be an endothermic reaction, in contrast to the highly exothermic oxidation of a phosphine with its associated very strong P—O bond (Table 13). 

Amine compounds including primary amines and amine-aldehyde condensation products are commonly utilized as fuel sweetening applications. Primary amines will react with H2S to form amine sulfide compounds. These products are somewhat unstable and may tend to solubilize into water. 

The orbital assignments of the first ionization potential, as well as of the higher bands which are broader and less intense, have been confirmed by ab initio MO calculations and by comparison with PE spectra of other small-ring cyclic ethers, amines, sulfides, silanes and cycloalkanes (77JA3226). 

The shifts in the statistically weighted average e/b2 IE values compared to the IE value for the t2g MOs of Cr(CO)6 (8.40 eV) are in the order pyridine > amine > sulfide > phosphine. This order is similar to that observed for the shifts... 

TABLE 5. Oxidation potentials ( p/2) of amines, sulfides and phosphines bearing a trimethylsilyl... 

Ozone can be depicted as the resonance hybrid of canonical structures 152a-152d,635 and one might expect ozone to react as a 1,3-dipole, an electrophile, or a nucleophile. The electrophilic nature of ozone has been recognized in its reactions toward alkenes, alkynes, arenes, amines, sulfides, phosphines, and so on.636-640 Reactions of ozone as a nucleophile, however, are less well documented.641... 

In an opposite manner to bases such as 1 and 2 in terms of reactivity, polymer-supported tosyl chloride equivalent 14 is able to capture alcohols as polymer-bound sulfonates 15, which are released as secondary amines, sulfides and alkylated imidazoles with primary amines, thiols and imidazoles as nucleophiles in a substitution process (Scheme 6) [24]. This technique has further been extended for the preparation of tertiary amines [25] and esters [26]. Excess of amine was scavenged by polymer-supported isocyanate 16 [27, 28] while excess of carboxylic acid was removed by treatment with aminomethylated polystyrene 17. 

Hydrolysis Oxidation Photolysis Esters, lactones, amides, lactams, oximes, imides, and malonic ureas Amines, sulfides, disulfides, sulfoxides, phenol anions, thiols, nitriles, and catechols Aromatic hydrocarbons, aromatic heterocyclics, aldehydes, and ketones... 

The equilibrium constants with nucleophiles such as tertiary amines are so large, that carbenium ions practically do not exist. Thus, tertiary amines and pyridine apparently react with carbenium ions irreversibly and therefore terminate carbocationic polymerizations. Somewhat weaker nucleophiles such as 2,6-dimethylpyridine (lutidine), sulfides, and tris(p-chlorophenyl)phosphine are good deactivators in vinyl ether polymerizations because they react reversibly with monomer, thus maintaining a low concentration of carbenium ions without causing elimination. However, the equilibrium constants in styrene and isobutene polymerizations with amines, sulfides, and phosphines are too large to generate a sufficient stationary concentration of carbenium ions to complete polymerization in a reasonable amount of time. 

C3H9N [107-10-8]), and the industrially important hydrodimerization to produce adiponitrile (C6HgN2 [111-69-3 f) (25—27). Other reactions include addition of halogens across the double bond to produce dihalopropionitriles, and cyanoetliylation by acrylonitrile of alcohols, aldehydes, esters, amides, nitriles, amines, sulfides, sulfones, and halides. 

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